Majon Vegeta and SSj4 Goku: Complete the last chapter with 60% or more health for all cities.

Piccolo (Fuse with Kami form): Defeat Cell in Chapter 2-1.

Pikkon: Defeat Janemba in Chapter 2- 9.

Super Buu (with Gohan absorbed form): Complete Chapter 7-3.

Super Buu (with Gotenks absorbed form): Complete Chapter 7-2.

Teen Gohan (Super Saiyan form): Defeat Cell in Chapter 3-8.

Teen Gohan (Super Saiyan 2 form): Defeat Teen Gohan in Chapter 3-9.

Vegeta (Majin form): Defeat Vegeta in Chapter 4-7.

Vegeta (Super Saiyan form): Defeat #18 in Chapter 2-3.

Vegeta (Super Saiyan 2 form): Defeat Janemba in Chapter 2-7.

Vegeto and Gogeta: Complete the last chapter choosing either path.

Vegetto (on all modes): Defeat Super Buu on Chapter 6 bottom path.

Vegetto (Super Saiyan form): Defeat Kid Buu in Chapter 5-B-9.

Vegito: Complete all seven chapters.

Hints

Transform during game play

Highlight a character that can transform and press Right. Choose your transformation state. Then, fill your Kai meter to just over half. Press Down + Circle and your character should transform. Note: If you get hit with no Kai remaining you can transform back into your normal state.

Defeating Kid Buu

To defeat Kid Buu, use melee attacks and do not let him regenerate himself. If you cannot avoid this, keep using your ultimate attack until he is dead. You must defeat him four times because of The Senzu Beans.

Glitches

Two Spirit Bombs

This trick only works in Training mode. Select Goku
as your character and anyone as the opponent. Once you are in
training, set the opponent to "Do Nothing" and set their
Ki Blast Defense option to "Deflect-Back". Then, throw
a Ki Blast at them, wait a moment, then press Up + Circle
to do your Spirit Bomb, but do not charge it up. If timed correctly,
the attack will fly over the Ki Blast that your opponent has deflected
back to you, and they will begin to take damage from your attack
while the Ki Blast comes toward you. Once the deflected Ki Blast
hits you, quickly press Select to refill your energy. Before
your super move is completely finished hitting your opponent,
prepare another, but fully charged. Your opponent will suddenly
stop taking damage, and your previous attack will disappear. Once
your fully charged attack starts flying toward your opponent,
watch the attack closely. As soon as your opponent starts getting
hit by your attack, you should see a second Spirit Bomb separate
from the first and fly past your opponent then explode. You can
also do this with anyone else who has an "Energy Ball"
supermove except for Kid Buu. It does not work with him because
he is so short that whenever you do the first one, it always flies
too low and cuts through the Ki Blast. Also, remember to throw
a Ki Blast at the beginning; if it doesn't hit you, you will
enter a "recovery time" after launching the attack where
you will not be able to move.